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United States Patent 3,189,594 HETEROGENEOUS COBALT COMPLEX COMPOUNDSReinhard Neier, Basel, Switzerland, assignor to Sandoz Ltd., Basel,Switzerland No Drawing. Filed Apr. 1, I963, Ser. No. 269,709 Claimspriority, application Switzerland, Apr. 11, 1962, 4,432/ 62 6 Claims.(Cl. 260-145) This invention relates to heterogeneous cobalt complexcompounds of monoazo dyes, one of the said monoazo dyes being of theformula on NH? r N X H I SOrNH-CH;C H- C H N O z wherein X representshydrogen, halogen, alkyl or alkoxy and the Nl-I group is in the adjacentposition to the N N- group, and the other monoazo dye being a member ofthe ortho,ortho'-dihydroxy-benzene-azonaphthalene series, preferably amember of the ortho,ortho'- dihydroxy-benzene-azonaphthalene series ofthe formula OH CIJH wherein V, Y and Z represents hydrogen, halogen,alkyl, alkoxy, nitro, or sulfonic acid amide which may be furthersubstituted and W represents hydrogen or car-boxylic acid amide whichmay be further substituted,

the monoazo dye of Formula II containing not more than two alkoxy-,nitroor sulfonic-acid amide groups, and cobalt, less than two cobaltatoms being in complex com bination with two molecules of azo compound.

These new heterogeneous cobalt complex compounds can conveniently beprepared by treating monoazo dyes in substance or on the fiber with acobalt-yielding agent, one of the said dyes being of the formula OH onwherein V, Y and Z represents hydrogen, halogen, aJkyl, alkoxy,

nitro, or sulfonic acid amide which may be further substituted and3,189,594 Patented June 15, 1965 W represents hydrogen or carboxylicacid amide which may be further substituted,

the monoazo dye of Formula II containing not more than two alkoxy-,nit-roor sulfonic-acid amide groups, 'so that a mixture ofcobalt-containing monoazo dyes is formed in which less than two cobaltatoms are in complex combination with two molecules of monoazo compound.

The metallizing reaction is preferably performed in such a way that anamount of a cobalt-yielding agent containing less then two but at leastone cobalt atom acts upon two molecules of the azo compound. Thereaction is conducted preferably in an aqueous, alkaline or organicmedi-' um to which the metal compound is added in the presence ofcompounds which maintain the metal dissolved in complex combination incaustic-alkaline medium, e.g. tartaric, citric or lactic acid.

Cobaltous formate, cobaltous acetate and cobaltous sulfate are examplesof suitable cobalt compounds.

Especially valuable heterogeneous cobalt complex compounds are obtainedwhen two monoazo compounds containing two groups capable of metalcomplex formation, of which at least one is a monoazo compound of theFormula I and the other an ortho,ortho'-dihydroxy compound of thebenzene-azo-naphthalene series which may be substituted, e.g. a mixtureof two monoazo compounds having the formulae:

mulae:

and

are treated with a cobalt-yielding agent.

The mixing ratio of any one of the dyes of Formula I and of a monoazodye of the ortho,ortho-dihydroxybenzene-azonaphthalene series may bevaried within wide limits. In most cases equimolar amounts of the twodyes are jointly metallized, though mixtures containing 20-80mol-percent of a dye of Formula I can be used.

Cobalt complexing of two monoazo compounds contain- EXAMPLE .1 V V 22.3parts of the dye produced by coupling'diazotized2-amino-1-hydroxy-5-nitrobenzene with Z-aminonaphthalene-6-sulfonicacid-(2' hydroxy)rpropylamide in acid ing groups capable of metalcomplex formation, of which 5 mediumrand 155 parts of the dye formed bycoupling of at least one 'is a monoazo compound of Formula I,'y1eldsdiaZOtI-Zed 2 anm-I1O l hydl.oxy 5 nitmbenzene and valuableheterogeneouscobalt complex dyes whose shades dmxynaphthakne in alkaline medium, aredissolved in and dyeing propemgsfmn be largelyadiusted to a speclal 1000parts of water at 70 containing 15 parts of sodium by changmg themtmerof 9 fzompmmds" hydroxide. A solution of 14.1 parts ofcrystallizedco- The heterogeneous cobalt-containing azo dyes produced 10baltous sulfate and Parts of tartaric acid in 100 parts in substance oron the fiber are well soluble in water and of water is added Thereaction mass is Stirred at 70 dye W001: 511k leather a Polygmlde fibersfrom neutral until the metal-free starting dyes are no longer indicated.to Weakly dyebaths grey blue and brown shades V The cobalt-containingdye formed is precipitated by the havlng good hght fastness and good wetfas nfi P Q addition of sodium chloride, filtered off, dried and ground.fies, fasmess to Washmg, Water f perspfra' It is obtained asra' darkpowder which dyes wool, silk, carbomzmg, Pleiachmg, mining; mbbmgPressmg, leather and polyamide fibers in blue shades. Owing'to itsaclds: alkahs: Stovlng and Y P l notable good solubility inorganicsolvents such as ketones, al-

I features of the dye are shght sensmvlty to hard cohols and acetic acidalkyl esters, it is also suitable for I *water and their suitability forhigh-temperature 'dyemg. 2O tha dyeing f organic flb fo i g materials591111 f The heterogeneous cobfllt-colltammg y Produced m solution inthese solvents, e.g. cellulose acetate and poly:

Stance are also well Soluble in P Solvents, ketolles, acrylonitrile. Itcan be used further tor the coloration 816011015 acetic acid alkylesters 8 3N of plastics and lacquers, e.g. vinyland nitrocelluloselacethanol, acetone, acetic acid ethyl ester, propionic acid queys, i blh d V V ethyl ester, amyl acetate etc. They are therefore 'well 'suit- Ith f ll i t bl the tructure of some further able for the y and Punting Qleatherf; f fiber-fofmheterogeneous cobalt complex dyes 1s shown.- Incolumn ing materials in solution in organic solvents, and of plas- (I)is listed the amount of the first monoazo'dye used,

tics and lacquefslill which matenals y glve y, blue in column (11). itsstructural constitution is given, in colafld brown Shades of good lightand Wet fastfless P P S- Hum (HI) the amount of the second monoazo dyeused,

In the following examples the parts and percentages 30 in column (IV)its composition, and in column (V) the are by weight and thetemperatures in degrees centigrade. shade of the dyeing of the cobaltcomplex dye on wool.

Table Example Parts Monoazo compound of formula (I) Parts Metallisableazo compound of any desired Shade of dye N o. constitution ing on wool 222.3 2-am ino-l-hydroxy--nitrobenzene 2-amino- 14.92-amino-1-hydroxy-Lchlombenzeneez-hydroxy- Blue-violet.

naphthaJene-G-sulfdnic acid-(2-hydroxy)- naphthalene. propylamide.

3 22.3 2-amino-l-hydroxy-4 uitrobenzenel-amino 26.9Lamina-LbydroxybenzeneA-sulfonic acid-(2- Grey-violet.

' naphthalene-Lsulionic acid (2-hydroxy)-carboxy){shenylamide-fl-hydroxydpropylamide. acetylaminonaphthalene.

4 V 24 2-amino-1-hydroxy-4-chloro-5-nitrobenzene-0- 15.52-amino-1-hydroxy-5-nitrobenzene 2-hydroxy- 'Blue.

amiuouaphthalene-E-sulfmfic acid-(2- naphthalene. hydroxy)-propylarnide.

5 23 2-amino-l-hydroxy-4-nitro-6-methylbenzene 1- 20. 8Zamino-l-hydroxybenzene4-sulfonic acid-Reddishaminonaphthalene-fi-sulfonic acid-(2-hy-(3'-methoxy)pmpyIamideAZ-hydroxygrey. droxy)-pr0pylamide. naphthalene. V

6 22.3 2-amino1-hydr0xy-5-nitrobenzol 2-amino- 16.52-amino-1-hydr0xy-4-chloro-5-nitl'obenzene- 2- Blue.

naphthalene-55111031110 acid-(2-hydroxy)- hydroxynaphthalene.propylamide.

'Z 22.8 do a 25 2-amino-1-hydroxy-5-nitrobenzene 2-hydroxy- Do.

' naphthaleuett-carboxylic acid-(3-sulfamid0)- phenylamide.

8 23.7 2-amino-1-hydroxy-4-methoxy5-nitr0benzene 18.32-21111110-l-hydIOXy-3,4,6-tIiGh101'ObGIlZ8DB- Do.

2-aminonaphthalene-6-sulfonic acid- (2-hy- 2-hydroxynaphthalene.

' droxy)-propy1amide.

9 33.4 2-ami11o-1-hydr0xy-5-nitrobenzene-d-amlno- 7.52aminc-1-hydroxy-benzene 2-hydroxynaph- Do.

naphthaleneA-sullonic acid-(2-hydroxy)- thalene. propylamide. V

10 29.6 d0 9.4 Z-amino-l-hydroxy-4-methylbenzene 2 D0.

hydroxynaphthalene.

11 22.3 do 14.7 2-amin0-1-hydro1q7-4-methoxybenzene 2- D0.

hydroxynaphthalene-3-carboxylic acidphenylamide.

12 22.3 2-amiu0-1-hydroxy-4-nitro-6-bromobenzene- 16.62-annno-1-hydroxy-4-bromobenzene 2- D0.

l-aminonaphthalene-B-sulfonic acid-(2- hydroxynaphthalene.hydroxy)-propylamide. 7

13 22.3 2-amino-1-hydroxy-5-nitrobenzene- 2-amino- 20.12-amjno-l-hydroxybeuzenel-sulfonic acid Violet.

naphthalene-.S-sulfonic acid-(2-hydroxy)- methylarnide2-hydroxynaphthalene-3- propylamide. carboxylic acid-methylamide.

14 33.4 rln 13.4 2-amino-l-hydroxybenzeneA-sullonjc acid- Blue.

amide- 2-hydroxynaphthalene-3-carboxylic v acid-amide.

15 24' 2-amino-1-hydroxy-4-chloro-5-n1trobenzene 162-amino-l-hydroxy-4tert.butylbenzene 2- Violet-blue.

1-amj11ouaphthalene-l-sulfonic acid (2- hydroxynaphthalene. Vhydroxy)-propylamide.

36 2am.ino-1-hydroxy-4-chloro-5 nitrobenzene- 12. 422mino-1-hydroxy-4-chlorobenzene-esulfonic Blue.l-aminenaphthaleneA-sulfonic acid-(2- acid phenylamide-2-hydroxynaphthaleue-3- V hydroxy)-propylamide. carboxylic acid-amide. Y

36 d0 8.1 2-amino-1-hydroxy-4ethoxybenzene 2- Do.

* hydroxynaphthalene.

24 do 22. 4 2-amin0-l-hydroxy-4,6-dinitrobenzene 2- Blue-grey.

hydr0xynaphthaleue-3-carb0xylio acid- (2- 1 hydroxy)-propylamide.

24 2-amiuo-1-hydr0xy-4-chlo1'0-5mtr0beuzenee 18.9Z-amino-1-hydroxy-4,6-dichlorobenzene 2- Blue.

l-aminonaphthalene-E-sulfonic acid (2- hydroxy-fi-methoxynaphthalene.hydroxy)-propylamide.

r 36 12.7 2-amino-1-hydroxy-5-nitrobenzene-+2-hydroxy- Do.

naphthalene-3-carboxylic acid phenylamide- I 3-sulfonieacid.

DYEING EXAMPLE A I part of the dye obtained according to Example 1 isdissolved in 4000 parts of water at 40-50" C. 100 parts of previouslywetted wool are entered into this solution and 2 parts of acetic acidare added dropwise; then the bath is heated to 100 over 30 minutes andheld at this temperature for 1 hour. The dyed wool is removed from thebath, rinsed with water and dried. A blue dyeing is obtained which hasexcellent fastness to light, washing, milling and perspiration.

DYEING EMMPLE B 100 parts of secondary cellulose acetate with a contentof 545 5 splittable acetic acid are dissolved in 300 parts of solvent,e.g. a mixture of 275 parts of acetone and 25 parts of methanol, and thesolution left overnight to swell.

1 part of the dye obtained according to Example 1 is dissolved in thesame solvent mixture. This solution is added to the cellulose acetatesolution and the whole stirred until 60 parts of solvent haveevaporated. The solution is filtered through cotton and a filter pressand spun as filament in the same Way as nncoloured cellulose acetatedope. The filament is dyed to a fast blue shade.

DYEING EXAMPLE C A lacquer is prepared with 20 parts of the vinylchloride-vinyl acetate copolymer composition Vinylite VMCH (registeredtrademark of Union Carbide Corporation), 70 parts of methylethyl ketoneand parts of ethylene glycol. 0.5 part of the cobalt-containing dyeobtained according to Example 1 is stirred into 10 parts of this lacquerand diluted with 25 parts of a 1:1 mixture of methyletllyl ketone andcyclohexanone. The colored lacquer is applied to aluminum foil and airdried. It is of blue color and has good light fastness.

DYEING EXAMPLE D A dyebath is prepared with 0.1 part of the monoazo dyeproduced from diazotized Z-"amino-l-hydroxy-4-nitrobenzene by couplingin acid medium with l-aminonaphthalene-4-sulfonicacid-(2'hydroxy)-propylamide, 0.1 part of the monoazo dye obtained bycoupling diazotized 2- amino-l-hydroxybenzene 4 sulfonic acid-(2-carboxy)- phenyl amide with 7-hydroxy-l-acetylaminonaphthalene inalkaline medium, 0.4 part of ammonium sulfate, 0.1 part of cobaltoussulfate and 1000 parts of water. 10 parts of Wetted-out Wool are enteredinto the bath at 40. The temperature is increased to 100 in 20 minutesand this temperature maintained for 1 hour. During dyeing 2 parts of 10%acetic acid are added dropwise and the evaporated water is replaced fromtime to time. On com pletion of dyeing the wool is removed, rinsed anddried. It is dyed to a violet-grey shade.

Nylon and other polyamide fibers are dyed in the same way as wool. Silkalso is dyed like wool except that the temperature of the dyebath is notallowed to exceed 90. Leather and paper are dyed by the methods normallyused in practice.

Formulae of representative dyes of the foregoing Examples are asfollows:

EXAMPLE 1 The 1:2 heterogeneous cobalt mixed complex compounds obtainedfrom the mixture of the monoazo dyes of the formula (I)H 1Y1'Hz N: zNl iI OH OH OH in the metal complex form and EXAMPLE 2 The 1:2 heterogeneouscobalt mixed complex compounds obtained from the mixture of the monoazodyes of the formula in the metal complex form and EXAMPLE 4 The 1:2heterogeneous cobalt mixed complex compounds obtained from the mixtureof the monazo dyes of the formula in the metal complex form and 7EXAMPLE 6 The 1:2 heterogeneous cobalt mixed complex compounds obtainedfrom the mixture of the monoazo dyes t v of the formula OH I 8 7 H 7OZNO sozNH-oH1oHoH3 a V I n; on v k in the metal complex form EXAMPLE 7The 1:2 heterogeneous cobalt 'mixed complex compounds obtained from themixture of the monoazo dyes of the formula and l I I V O 2N -SI 0 2 NH:

in the metal complex form V t SOT- HL c Having thus disclosed theinvention what I claim is: 1. A 1:2-heterogeneous cobalt mixed complexof the formula 7 tZ-aminQnaphthaIene-S -sulfonic acid- (2'-'hydroxy) Vpropylamide, and a 1-aminonaphthalene-S-sulfonic acid-(ZFhydroxy)?propylamide,

and wherein the O- group of the diazo component and; the NH- groupof'the coupling component each stands in the adjacent position to the-N=N- group, and the other monoazo radical being a monoazo 'dye radicalof the ortho, ortho'-dihydroxybenzene-azonaphthalene series of theformula 7 D is a member selected from the group consisting of theradicals of diazotized Z-amiuo-l-hydroxy-nitrobenzene,Z-amino-l-hydroxy-ehlorobenzene,

2 amino 1 hydroxybenzene-sulfonic acid-(car V boxy)phenylarnide,

2-amino 1 hydroxybenzene-sulfonic acid-(lower a1koxy)lower alkylamide, ta T r 2-amino-l-hydroxy-chloro-nitrobenzene,

do) phenylamide,

2-hydroxynaphthalene 3 carboxylic acid-phenylamide,

2-hydroxynaphthalene-3carboxylic acid-lower alkylamide,

2-hydroxynaphthalene-3-carboxylic acid amide, 2 hydroxyn-aphthalene 3carboxylic acid-(hydroxy)-lwer alkylamide, 2-hydroxy-6-loweralkoxynaphthalene, and 2-hydroxynaphthalene-3carboxylic acidphenylamide-sulfonic acid and wherein the O groups in the diazo andcoupling component each stands in the adjacent position to the -N=Ngroup.

2. The 1:2 heterogeneous cobalt mixed complex of the formula 3. The 1:2heterogeneous cobalt mixed complex of the formula 4. The 1:2heterogeneous cobalt mixed complex of the formula 5. The 1:2heterogeneous cobalt mixed complex of the formula 6. The 1:2heterogeneous cobalt mixed complex of the formula References Cited bythe Examiner UNITED STATES PATENTS CHARLES B. PARKER, Primary Examiner.IRVING MARCUS, Examiner,

4/54 Widmer et al 260151 6/58 Neier 260151 XR

1. A 1:2-HETEROGENEOUS COBALT MIXED COMPLES OF THE FORMULA